Process of making cyclic ketones.



UNITED STATES Patented July 19, 190% PATENT OFFICE.

PHILIPPE CHUIT, OF GENEVA, SWITZERLAND, AND FRITZ BACHOFEN,'OF NEW YORK, N. Y.,' ASSIGNORS TO THE FIRM OF CHUIT NAEF & CO.,

OF GENEVA, SWITZERLAND' PROCESS OF MAKING CYCLIC KETONES.

SPECIFICATION forming part of Letters Patent No. 765,459, dated July 19, 1904.

Application filed February 9, 1903.

To all whom it may concern:

Be it known that we, PHILIPPE CIIUIT, residing at the Usine de la Queue dArve, Geneva, Switzerland, and FRITZ BAGHOFEN, residing at the Helvetia Chemical Company, Platt street, New York, State of New York, have invented new and useful Improvements in Processes for the Transformation of Hydrolized Pseudoionone and its Homologues into 0 Cyclic Ketones, of which the following is a specification.

The hydrolized pseudoionone and its homologues themselves may no doubt be obtained by various methods; but they are very easily I5 obtainable by the action of concentrated acids, preferably phosphoric or sulfuric acids, at a low temperature on pseudoionone or its homologues, not as has hitherto been done viz by adding the pseudoionone gradually to the.

cooled acidbut, on the contrary, by letting the acid run drop by drop into the pseudoionone kept cooled, the mixture being constantly agitated. It has been ascertained that under these conditions the pseudoionone and its homologues are transformed into new-derivatives by water fixation. This transformation takes places with an excellent yield.

It is important to operate as indicated in order that the pseudoionone or one of its homo- 3 logues methylpseudoionone, dimethylpseudoionone, &c.according with which one operates, shall not at the beginning of the transformation be brought into contact with a large excess of acid, which would of course occur if one of these products was gradually added to the acid, and, on the other hand, it is also advantageous to use a smaller quantity of acid than that generally employed to obtain ionone. The formation of such hydrolized products as 4 intermediate products between pseudoionone and ionone has been hypothetically admitted by Barbier and Bouveault (monohydrolized product) and Tiemann and Kruger, (dihydrolized product.)

The by drolized product from pseudoionone,

Serial No. 142,689. (No specimens.)

with the following formula C13H22O2, is a yellowish liquid, thick and syrupy at ordinary temperature, nearly odorless, with a density of 0.960 at 15 centigrade. It distils at 17 6 to 178 centigrade (n. 0.) under 9 millimeters pressure and yields a semicarbazone melting at H L centigrade. I

The hydrolized methylpseudoionone prepared with methylpseudoionone of 0.896 density at 20 centigrade obtained by condensation of citral and methylethylketone by means of condensing agentssuch as ethylate of sodium, peroxid of sodium, or sodium amidpose sesses a density of 0.950 at 20 centigrade and boils at 186to 192 centigrade (n. 0.) under 12.5 millimeters pressure. Its semicarbazone is for the most part oily. I The methylpseudoionone the density of which is 0.912 at 20 centigrade, which is also obtained from citral and from methylethylketone, but by using a light solution of caustic soda as condensing agent and which is a mixture of several bodies, gives a hydrolized methylpseudoionone with a density of 0.956 at 20 centigrade and boiling at about 190 centigrade under 13.5 millimeters. This hydrolized methylpseudoionone yields abundantly with the semicarbazid asemicarbazone well crystallized and melting at 193 centigrade.

We have ascertained that the hydrolized products from the pseudoionone and its homologues may be easily transformed into cyclic derivatives containing one molecule less of water and are consequently excellent raw products to prepare the alpha and beta ionone or their homologues, which are thus obtained with an excellent yield and nearly free from hydrocarbids and resins, which always accompany these bodies when prepared directly ,from their pseudoionones. Among the bodies which easily provoke this transformation into cyclic ketones are, in the first place, concentrated phosphoric, formic, and sulfuric acids.

Example: (a) Two hundred and fifty parts of hydrolized pseudolonone are added gradu- Distilling Dengity alt Semicm ba |P br phenyl ally while constantly agltatlng to twelve hunpoint. 29 g? zones. hydrazone. dred and fifty parts of syrupous phosphoric acid placed into a cooling mixture. The hy- Alpha. 138 up 143 0.931to0.932. Few crystals Oily. drolized pseudoionone dissolves entirely with- $335113 1.51331 out causing much heating of the mixture, i fi g i gg ig 'fg g which becomes very tlliCk. The mixture lS pressure. (Ier of the 60 left for half an hour, and then the tempera- ,222.15 if; ture is raised up to centigrade by warmgggfi ggfl IO ing the receptacle in which one operates from o r 0 tain time.

theoutside. Themixtureisafterward poured ,55 ,319, 3 ggggggggg; Ollyover ice and water. A thick syrupy brownf g- 3 5 ggg g ish body separates itself, but is shortly afterlimeters ward transformed by the action of the water Pressure 5 into a yellow oil, which is distilled in steam after having previously been washed with The 337C ketones sr m hydrohzed water and afterward with carbonate of soda. rneoth-vlpwdolonone Wlth adenslty of 0956 at 7 The raw oil which is obtained dried in vacu- 20 cenfilgl'ade (W D l P the y um possesses a d i f 935 at centi pseudolonone with a density of 0.912, Whlch 2o gradeand Once d ll d in Vacuum h d 1s a mixture of several bodies) have the folsity is 0.933. It isnearly pure alpha-ionone. lowmg propertles:

(1)) One hundred parts of hydrolized pseu- 75 v.-. Distillin Denslty Semic'n'ba- P brhen '1- doionone are mixed with five hundred parts boiling 20 ce t -.g, g of formlc acid. (one hundred per cent.) The 5 Q Whlch becomes 3 (31631 Wlthoul} Alpha. 134 to 138 0.933to0936. Melting at Melting at becoming Warm, 1s afterward heated for half centlsmde t F (n. 0.) un- Centigrade. centlgrade. an hour on a Water-bath, then poured lnto (1 e113 mil- 80 water and treated as above. Thus also par- 1, 35,335; ticula rlv alpha-ion0ne is btained Beta 132 {30 0.939170 0.943. At centi 135 to 136 Centigrade grade. Centigrade. 3 (0) Two hundred and fifty parts of hydro- (11. 0.) unllzed pseudolonone are poured drop by drop f f fg lnto twelve hundred and fifty parts of sulfuric p essure. 85 acid (seventy-five per cent.) cooled 111 a wing crating mixture, care being taken to con- We clalm as our lnventlon 35 stantly stir the mixture during the addition. The hereln-descrlbed process for the prepa- This ended, it is left for an hour. Then the ration of cyclic ketones, consisting in reacttemperature is raised to 20 centigrade and ing on hydrolized pseudoionone and its homo- 9 the whole poured over a mixture of ice and logues with concentrated acid, washing the water. The oil thus obtained after being disproducts from the reaction with water, and

4 tilled in'steam has a density of 0.940 at 20 then distilling said products to purify them, centigrade. It distils in vacuum without leavsubstantially as and for the purposes set forth. ing any residue. It is a body largely com- In testimony that we claim the foregoing as 95 posed of beta-ionone. The homologues of the our invention we have signed our names in hydrolized pseudoionone treated with the presence of two subscribing witnesses.

45 same acids in a similar Way also yield cyclic 1 derivatives which are also homologues of alpha and beta ionone, according to whether phosphoric, formic, or sulfuric acid is used. Witnesses as to signature of Philippe Chuit:

The alpha and beta methylionone derived T. FIRMowIoH, 5 from the hydrolized methylpseudoionone of G. IMER.

a density of 0.950 at 20 centigrade (corre- \Vitnesses as to signature of F. Bachofen: sponding to the methylpseudoionone of 0.896 GEO. TQPINOKNEY,

density) have the following properties: S. T. HAVILAND. 

